Microscopic Mechanisms of Glass-Like Lattice Thermal Transport in Cubic Cu$_{12}$Sb$_{4}$S$_{13}$ Tetrahedrites (2004.07343v2)

Abstract: Materials based on cubic tetrahedrites (Cu${12}$Sb${4}$S${13}$) are useful thermoelectrics with unusual thermal and electrical transport properties, such as very low and nearly temperature-independent lattice thermal conductivity ($\kappa{L}$). We explain the microscopic origin of the glass-like $\kappa_{L}$ in Cu${12}$Sb${4}$S${13}$ by explicitly treating anharmonicity up to quartic terms for both phonon energies and phonon scattering rates. We show that the strongly unstable phonon modes associated with trigonally coordinated Cu atoms are anharmonically stabilized above approximately $100$ K and continue hardening with increasing temperature, in accord with experimental data. This temperature induced hardening effect reduces scattering of heat carrying acoustic modes by reducing the available phase space for three-phonon processes, thereby balancing the conventional $\propto T$ increase in scattering due to phonon population and yielding nearly temperature-independent $\kappa{L}$. Furthermore, we find that very strong phonon broadening lead to a qualitative breakdown of the conventional phonon-gas model and modify the dominant heat transport mechanism from the particle-like phonon wave packet propagation to incoherent tunneling described by off-diagonal terms in the heat-flux operator, which are typically prevailing in glasses and disordered crystals. Our work paves the way to a deeper understanding of glass-like thermal conductivity in complex crystals with strong anharmonicity.